EP2334596A2 - Composition à base de phosphate ferrique, préparation et applications associées - Google Patents

Composition à base de phosphate ferrique, préparation et applications associées

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Publication number
EP2334596A2
EP2334596A2 EP09776306A EP09776306A EP2334596A2 EP 2334596 A2 EP2334596 A2 EP 2334596A2 EP 09776306 A EP09776306 A EP 09776306A EP 09776306 A EP09776306 A EP 09776306A EP 2334596 A2 EP2334596 A2 EP 2334596A2
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EP
European Patent Office
Prior art keywords
composition
timber
iron
mass fractions
aluminium
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EP09776306A
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German (de)
English (en)
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EP2334596B1 (fr
Inventor
Gennadi Nikolaev
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Individual
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
    • C23C22/08—Orthophosphates
    • C23C22/18—Orthophosphates containing manganese cations
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/26—Phosphorus; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/37—Phosphates of heavy metals
    • C01B25/375—Phosphates of heavy metals of iron
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/02—Inorganic materials
    • C09K21/04—Inorganic materials containing phosphorus
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/166—Compounds of phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/26—Compounds of iron, aluminium, or chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/16—Inorganic impregnating agents
    • B27K3/32—Mixtures of different inorganic impregnating agents

Definitions

  • the invention deals with a phosphate based composition, which can be used for the bio- and fire protection of timber, as an antibacterial disinfectant, as well as a rust converter for the corrosion protection of metals.
  • a phosphorus compound and the use thereof are known (US patent 6350474 Bl, AOlN 59/00, David Dzneladze et al., 2002), whereas the composition of the phosphorus compound is: orthophosphoric acid 100 mass fractions, iron oxide 20-41 mass fractions, aluminium powder 0.5-2.5 mass fractions, water 30-70 mass fractions.
  • orthophosphoric acid 100 mass fractions
  • iron oxide 20-41 mass fractions iron oxide 20-41 mass fractions
  • aluminium powder 0.5-2.5 mass fractions
  • water 30-70 mass fractions To obtain the compound, water and iron oxide and aluminium powder are mixed with orthophosphoric acid, whereby an exothermic reaction takes place. The heat released is sufficient to dissolve the iron oxide and aluminium powder.
  • the phosphoric compound obtained is absolutely harmless to nature. It can be used as an impregnating agent to increase the fire resistance of materials, as well as to increase the strength and heat resistance of concrete and ceramics, as a preservative, as a rust- inhibiting agent.
  • a disadvantage of the compound is its relatively low stability and low wetting capacity, which impede a broad use of the compound.
  • a phosphoric compound is also known (utility model EE 00444 Ul, AOlN 59/26, Gennadi Nikolaev, 2004), which is distinguished by the fact that, in order to increase its stability and wetting capacity, amounts of orthophosphoric acid, iron oxide, aluminium powder and water with ratios known from US patent 6350474 Bl are mixed and 0.05-0.2 mass fractions of either ethyl alcohol or glycerine are added to the mixture.
  • a disadvan-tage is the low fire resistance of materials covered with the compound, for example timber, paper, textile and metal surfaces, and inadequate protection against rotting and humidity.
  • the task of this invention is to obtain an ferric phosphate based composition, the use of which increases substantially the fire resistance and bio-protection of materials containing cellulose.
  • the task set is solved in such a manner that in the ferric phosphate based composition, to obtain which 100 mass fractions of orthophosphoric acid is mixed with water, iron oxide and an aluminium source, using powdery Al 2 O 3 in the amount of 5-10 mass fractions as the aluminium source, thereby maintaining the reaction temperature within a range of 60- 70 0 C. Due to an exothermic reaction no additional energy source is necessary to dissolve the components.
  • the amount of the iron oxide constitutes 10-20 mass fractions and the amount of the water 100 mass fractions, whereby the composition is distinguished by the fact that at least one nanopowder from among silver, copper or flint in the amount of 0.5 mass fractions is added to the mixture. Due to the proportions of the components according to the invention, the relative percentage of the aluminium oxide increases, which improves the properties of the final concentrate substantially, as a result of which the fire and bio-resistance of materials containing cellulose covered with the said composition increases.
  • the iron sulphate composition according to the invention forms in the course of the following chemical processes.
  • the reaction takes place in a temperature range of 60-70 0 C and it is controlled by the amounts of the aluminium oxide and nanopowders added.
  • the reaction product is iron(III) dihydrogen phosphate dihydrate Fe(H 2 PO 4 ) 3 x 2H 2 O in the form of liquid.
  • One of the distinguishable characteristics of this invention is increasing the amount of aluminium oxide to 10 parts of the overall mass.
  • This constituent is known to act as a catalyst, modifying the speed of chemical and physical processes towards the direction given.
  • the main function of the aluminium oxide in the invention based process is to facilitate the formation of intermediate compounds between the phosphate and iron with higher reactivity in the course of the synthesis, which allows reducing activation energy and facilitates the formation of the compounds with the given structure. In this case it increases the speed of the synthesis reaction and the preparation time of the composition reduces from 4 hours to 2 hours.
  • the increased amount of the aluminium oxide in the composition reduces such an important indicator as the acidity of the finished mixture, with pH value changing from 0.2 to 1.
  • Another distinguishable characteristic of the invention is adding nanopowdery components, such as Ag, Cu and flint, as a result of which the bactericide properties of the composition and the strength of the layer applied increase.
  • nanopowdery components such as Ag, Cu and flint
  • iron(III) dihydrogen phosphate dihydrate acts as a modifier by entering into a chemical reaction with the cellulose. At the modification the iron(III) dihydrogen phosphate dihydrate fixes to the timber surface and forms a protecting surface cover.
  • the composition can be used as a fire protective agent of timber and other materials containing cellulose.
  • the composition can be used for the bio-protection of timber against decay and rotting.
  • the composition can be used as a disinfecting antibacterial agent.
  • the composition can be used as a rust converter and a protecting agent against the corrosion of metals.
  • Example of practical performance 100 mass fractions of 85% orthophosphoric acid is poured into a reactor, then 100 mass fractions of water, 10-20 mass fractions of comminuted iron(III) oxide, 5-10 mass fractions of powdery aluminium oxide and nanopowders of silver, copper and flint comminuted to particles 50 to 100 nm in the amount of 0.5 mass fractions are added in the presence of constant mixing.
  • An exothermic reaction takes place, in the course of which the neutralisation of excess acidity and the dissolution of the metal oxides takes place.
  • the heat released at the exothermic reaction is sufficient to dissolve the iron oxide and aluminium powder.
  • the reaction temperature is controlled by the amount of the aluminium oxide added and it is maintained within a range of 60 to 70 °C.
  • a colloidal solution of the orthophosphates is obtained from the nano-iron, -aluminium and silver, copper, silicon metals, which comprise a composition of iron aluminium phosphate Fe(H 2 PO -I ) 3 and A1(H 2 PO 4 ) 3 with the particle sizes of the metals from 50 to 100 nm.
  • the composition obtained is in the form of a light brown, translucent, viscous liquid, which is handy to be used as a cover layer of materials.
  • the iron (III) dihydrogen phosphate present in the composition is a modifier of bio- and humidity protection for timber materials, which acts by entering into a chemical reaction with the cellulose. At the modification the iron (III) dihydrogen phosphate fixes on the timber surface.
  • the ferric phosphate based composition can be used as an impregnating agent to increase the fire resistance of timber and other materials containing cellulose, for the bio- protection of timber against decay and rotting, as a disinfecting antibacterial agent, as well as as a rust converter for the rust-inhibiting of metals.
  • the iron(III) dihydrogen phosphate dihydrate is not carcinogenic, it has no accumulating effect and it causes no local irritation.
  • Iron(III) forms a wide array of salts with phosphoric acid, including also Fe(H 2 PO 4 ) 3 .
  • These salts can be regarded as oxide mixtures with a generic formula Fe 2 O 3 x xP 2 O 5 x yH 2 O, where x and y are various integers.
  • the constitution Fe 2 O 3 x 3P 2 O 5 x 6H 2 O corresponds to the substance in the case of such a marking. It has also been proposed that the substance is actually ferriphosphoric acid with the constitution H 6 (Fe(PO 4 ) 3 .
  • Fe(H 2 PO 4 ) 3 x H 2 O(Fe 2 O 3 x 3P 2 O 5 x 10H 2 O) and FeH 3 (PO 4 ) 2 x 2,5H 2 O(Fe 2 O 3 x 2P 2 O 5 x 8H 2 O) have been described.
  • Fe 2 O 3 x XP 2 O 5 x yH 2 O one deals with a very complex system, obtaining individual salts from which is not easy (the liquid phases are viscous, the solid sediments present in them are hygroscopic).
  • the abovementioned data explain, why there is so little discussion about the substance Fe(H 2 PO 4 ) 3 and why a chemical seller does not offer the substance.
  • the substance is soluble in water, the aqueous solution of the substance being brownish.
  • the solution has a very complex constitution.
  • the product constitutes a viscous, fluid solution (soluble iron 48-60 g/1, soluble aluminium 24-30 g/1, soluble silver of nanopowders 2-3 g/1, orthophosphoric acid 320- 380 g/1), the rheology of which is mostly determined by its water content. It is a light brown colour, has a density of 1.47g/cm 3 , its viscosity being 34.3 on the basis of B3-4.
  • the composition obtained dissolves well in water, which allows using it extensively at the treatment of timber with a paint roller, brush, airbrush, as well as under pressure on industrial scales. At the drying of the binding agents protective coatings are formed, which are virtually ablation resistant, condense on the surface of the products as moisture, while the mechanical properties of the treated materials preserve for a long period of time.
  • the ferric phosphate based composition according to the invention showed that it has a wide area of application in the timber industry and building, veterinary medicine, agriculture and forest management, as well as at the production of building materials.
  • the composition has an anticorrosive effect on metals, it works as a bio-protection agent and can be used as a preservative in the case of timber.
  • An increase in the fire resistance of timber owing to the composition observed allows us to claim that it can be used as a antipyretic of timber.
  • the composition according to the invention is ecologically harmless, while with its help it is possible to protect the natural resources of a country (trees, metals, soil, water) against decay and pollution.
  • the ferric phosphate based product on sale is manufactured in a crystalline form and is used also as a food additive.
  • Brian Steinwand Biopesticides and Pollution Prevention Division (7511C), Office of Pesticide Programs Environmental Protection Agency, 1200 Pennsylvania Avenue, NW, Washington, D.C., 20460. Phone: 703-305-7973 (or 308- 8712). Fax: 703-308-7026.
  • E-mail steinwand.brian( ⁇ ),epa. gov.
  • the EPA Biopesticides Web site is: http://www.epa.gov/pesticides/biopesticides. Review report for the active substance ferric phosphate finalised in the Standing Committee on Plant Health at its meeting on 29 June 2001 in view of the inclusion of ferric phosphate in Annex I of Directive 91/414/EEC.
  • the major difference of the ferric phosphate based composition dealt with herein from similar goods manufactured in the world is that the composition is in the form of liquid, whereas the Chinese and American manufacturers sell ferric phosphate without additives and in a crystalline state.
  • the composition according to the invention is in a colloidal state and its constitution involves a wide array of metals of substantial importance; each one of them has its material importance, while they complement one another.
  • the liquid obtained is handy to preserve and transport, easy to use (dissolving with water is enough). It maintains its properties for up to 5 years, is not hazardous or carcinogenic, it is being used widely.
  • the technical properties are certified with production quality certificates of OU HoIz Prof. Its manufacturing does not generate hazardous waste or waste gases, is ecologically harmless to both people and animals, whereby the manufacturing of crystalline phosphates in China and the USA are accompanied by major problems related to hazardous waste and waste gases.
  • the main components of timber are cellulose, lignin and hemicelluloses (HMT), whereby their content varies on a relatively wide scale, depending on the type, age and habitat of the tree.
  • the cellulose content varies 40-60%, HMT - 13-25% in the case of coniferous trees and 25-35% in the case of deciduous trees.
  • the lignin content varies to a smaller extent: 18-25% in the case of deciduous trees and 26-35% in the case of coniferous trees.
  • the constitution of HMT and lignin is different in the case of deciduous and coniferous trees, as well as in the case of different layers of the tissues, cells and even cell membrane of the timber within one species.
  • the ferric phosphate based composition does not obstruct the breathing cycle of timber, does not block or conserve its pores, rather than blocks the enzymes and hinders the activity of microorganisms located on the timber or growing on it (spores of fungi decomposing timber.).
  • the composition creates a strong bond with timber, decreasing its porosity.
  • hydroxyl groups are characteristic functional groups of lignin and determine much its reactivity in delignification, condensation, oxidation processes and at the chemical modification of various derivatives.
  • the total hydroxyl group content forms one hydroxyl lignin per a structural unit of phenyl propane on an average.
  • a lignin macromolecule contains hydroxyl groups of different natures (aliphatic and phenol)
  • the lignin reaction centre blocking method was applied to examine the direction of the mutual effect of ferric phosphate with the hydroxyl groups of lignin.
  • the IK spectrum of lignin displays well an increase in the intensity of the absorption bands in the zone of the valence fluctuation of hydroxyl groups of 3,000-3,600 cm “1 and the lack of absorption bands of 1,660 and 1,715 cm “1 , which is responsible for fluctuations in carbonyl groups. It is concluded from these data that all types of hydroxyl groups of lignin participate in the phosphorylation reaction.
  • iron(III) dihydrogen phosphate dihydrate can enter into the walls of timber cells, fix there and simultaneously ensure the formation of a modified crystalline network, condensing it and filling in the gaps between the spaces.
  • the cell walls alter their state and the ferric phosphate is fixed there for a long period of time.
  • Orthophosphate compounds suit well for the modification of timber, whereas they are capable of forming compounds with hydroxyl groups of cellulose and simultaneously associate functional groups in the timber.
  • the source materials for modification can also be ammophos or carbamide as well as other non-organic compounds containing nitrogen or ammonia, which in turn contain the good compound put forward herein in the phosphate composition.
  • the deformation resistance, longevity, fire resistance and solidity of the timber By introducing phosphate compounds into timber, the deformation resistance, longevity, fire resistance and solidity of the timber, the ablation resistance of the phosphate composition of the timber increases, water absorption decreases, light resistance, light stability form, the resistance of the timber treated with this material to mould, colouring and timber decaying fungi and other micro-organisms damaging materials containing cellulose forms.
  • the results of these tests ascertain the modification of the timber with the ferric phosphate based composition according to the invention, its fixing in the timber and the achievement of high fire protection and bio-protection properties.
  • the constitution of this composition is as follows: iron(III) dihydrogen phosphate dihydrate - 20%, carbamide up to 2%, boric acid up to 2% and non-ionogenic PAV up to 0.2%.
  • the iron oxide, phosphoric acid and aluminium oxide affect the ratio of CO/CO 2 , inhibiting the oxidation of carbon into carbon dioxide, which decreases the exothermic effect of the process substantially.
  • the inorganic phosphate compounds inhibit the burning process of the cellulose. Phosphoric acid starts to dehydrate at 213 0 C, transferring into pyrophosphoric acid H 4 P 2 O 7 , which slowly transfers at 800 0 C into metaphosphoric acid HP 2 O 3 , thereby the said compounds do not escape at an active incandescence temperature (500-700 0 C). With the influence of the composition applied to the cellulose materials, the mechanism of their thermal decomposition cahenges.
  • the modifications of the cellulose in the presence of the iron, phosphorus and aluminium are characterised by the commencement of lower temperature destruction, an increase in the outputs of char and water at a smaller discharge of volatile, including combustible degradation compounds (carbon oxide, levoglucosan, etc.).
  • the antipyretic effect of the ferric phosphate based composition on the timber complex is mainly due to a rapid change in the mechanism of the thermal changes of the carbohydrate part of the timber complex. This catalyses the dehydration reaction of the cellulose. As a result of this, the effective energy of the activation of the dehydration process decreases, the temperature of the commencement thereof decreases, the speed and amount of the discharge of the water formed increase.
  • a special role in the phosphate composition is played by the nanometals of silver, copper and silicon dioxide, which perform their functions in timber protection - they are bactericidal and antiseptic - the silver and copper and the reinforcement of the upper layer and protection against ablation - the silicon.
  • the main peculiarity of the chemical properties of the nanoparticles of the metals is high reactivity, which is due to an increased proclivity towards an ion and atom exchange, adsorption on varied surfaces, the formation of superficial bonds with other adsorbing particles.
  • the studies were ascertained in a 2005 summary of the Nizhegorodsk State Medical Academy (US), where bactericidal and antiseptic qualities of even 2% solution are confirmed.
  • the precoat Lust is a primer, which is meant for treating timber prior to painting, protecting against rotting, decaying, mould and timber deconstructing fungi and timber eating insects, having antiseptic and antibacterial properties, disinfecting and protecting mineral bases, concrete, plaster and other building constructions against mould, consisting of 8% iron(III) dihydrogen phosphate dihydrate, 2% carbamide, 2% boric acid, up to 0.1% PAV. Certified on the basis of European standard EN 1276, a study by the Central Laboratory of Microbiology No.
  • All materials based on the ferric phosphate based composition require a certain procedure, which involves the cleaning of the treated spot from dirt, dust, bark, phloem, other coatings, then the timber surface is treated with a brush, paint roller, airbrush at an ambient temperature of no less than +5 C, at humidity of no more than 75%, as well as by immersion, soaking or autoclaving.
  • Applying with the brush, paint roller or airbrush is performed with takes, with a break of 20-40 minutes, ensuring standardised total consumption.
  • the soaking or impregnation in the autoclave is performed until reaching standardised consumption. Resistance to ablation forms within 7 days. Total consumption when applying with the brush, paint roller, airbrush - at least 200-300 g/m 2 (1 litre per 3-5 m 2 ); consumption at the soaking or autoclaving depending on the timber and the treatment quality thereof 40-100 kg/m 3 .
  • the constitution of this material involves iron(III) dihydrogen phosphate dihydrate 20%, orthophosphoric acid 20%, manganese oxide up to 0.1% and PAV.
  • the composition material according to the invention combines all properties to fight corrosion, it is a rust converter — removes a decomposed layer of iron by converting it into a protective layer of metal oxides, an inhibitor - a decelerator of corrosion, decelerates and stops the chemical reaction of iron decomposition, while being also a passivating agent - creates a film of soft and plastic aluminium, zinc and other metal oxides, which in aggressive environments undertakes the decomposing impact of corrosion in the first place and decomposes itself with the passage of time, yet protects the main metal from rusting, while being also a reinforcing additive of manganese and silicon on the upper layer, which prevents and protects from mechanical damage.
  • rust converter removes a decomposed layer of iron by converting it into a protective layer of metal oxides, an inhibitor - a decelerator of corrosion, decelerates and stops the chemical reaction of iron decomposition, while being also a passivating agent - creates a film of soft and plastic
  • the iron(III) dihydrogen phosphate dihydrate fixes to the timber surface and forms a protecting surface cover.
  • medicine cancer treatment; infections of nasal, auricular, laryngeal organs; inflammatory infections of the mouth cavity; bronchial-pulmonary diseases; diseases of the gastric-intestinal tract; prophylactics and fighting infection processes, which involve antiseptic lavage, application, water disinfection, food preservation, air filtering, antimicrobial protection of garments, footwear, household items; infectious damage of bones, bone marrow, muscles, joints, lymph nodes.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Metallurgy (AREA)
  • General Health & Medical Sciences (AREA)
  • Zoology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Forests & Forestry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Fireproofing Substances (AREA)

Abstract

La présente invention concerne une composition à base de phosphate ferrique. Afin d’obtenir cette composition, 100 fractions en masse d’acide orthophosphorique, 10-20 fractions en masse d’oxyde de fer (III), 5-10 fractions en masse d’oxyde d’aluminium en poudre et 100 fractions en masse d’eau sont mélangées, la réaction se produisant à une température variant de 60 à 70 °C et au moins une nanopoudre parmi l’argent, le cuivre et le silex étant ajoutée au mélange en quantité de 0.5 fraction en masse. Les compositions à base de phosphate ferrique peuvent être utilisées pour la protection biologique et contre l’incendie du bois en grume, comme désinfectant antibactérien, ainsi que comme convertisseur de rouille pour une protection antirouille des métaux.
EP09776306A 2008-08-22 2009-08-19 Composition à base de phosphate ferrique, préparation et applications associées Active EP2334596B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL09776306T PL2334596T3 (pl) 2008-08-22 2009-08-19 Kompozycja oparta na fosforanie żelaza (III) i jej zastosowanie

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EEP200800055A EE05408B1 (et) 2008-08-22 2008-08-22 Raudfosfaadip?hine kompositsioon, selle valmistamine ja kasutamine
PCT/EE2009/000012 WO2010020256A2 (fr) 2008-08-22 2009-08-19 Composition à base de phosphate ferrique, préparation et applications associées

Publications (2)

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EP2334596A2 true EP2334596A2 (fr) 2011-06-22
EP2334596B1 EP2334596B1 (fr) 2012-07-04

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US (1) US20110223258A1 (fr)
EP (1) EP2334596B1 (fr)
CN (1) CN102046526B (fr)
BR (1) BRPI0917821B1 (fr)
CA (1) CA2724190C (fr)
DK (1) DK2334596T3 (fr)
EE (1) EE05408B1 (fr)
ES (1) ES2391753T3 (fr)
GB (1) GB2475454A (fr)
PL (1) PL2334596T3 (fr)
WO (1) WO2010020256A2 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011086526A1 (fr) 2010-01-15 2011-07-21 Uusen, Tarvi Composition de phosphate de fer et procédé pour la préparation et l'utilisation de celle-ci
US9586070B2 (en) 2013-01-22 2017-03-07 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in solid materials

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101371356B1 (ko) 2012-08-10 2014-03-07 한국교통대학교산학협력단 pH 조절을 이용한 FePO₄제조 방법 및 이를 이용한 리튬이차전지 양극용 LiFePO₄/C 복합재 제조 방법
US9622483B2 (en) 2014-02-19 2017-04-18 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
US11039621B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
US11039620B2 (en) 2014-02-19 2021-06-22 Corning Incorporated Antimicrobial glass compositions, glasses and polymeric articles incorporating the same
CZ306249B6 (cs) * 2015-09-03 2016-10-26 Mendelova Univerzita V Brně Způsob ošetření a barvení dřeva obsahujícího třísloviny
DE102018105086A1 (de) * 2018-03-06 2019-09-12 Toru Sonoda Wirkstoffreservoir zum Speichern von wenigstens einem Wirkstoff, Set, Blasinstrument, Wirkstoffspeicheranordnung und Aufbewahrungsset

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH498947A (de) * 1967-11-15 1970-11-15 Klingler Adolf Verfahren zur Herstellung eines korrosionsfesten Überzugs auf Metallen, Mittel zu seiner Durchführung sowie eine Anwendung des Verfahrens und nach dem Verfahren mit einem korrosionsfesten Überzug versehenes Metall
US5279650A (en) * 1992-06-01 1994-01-18 Solar Turbines Incorporated Corrosion resistant seal coat composition and method of forming
EA000483B1 (ru) * 1996-06-14 1999-08-26 Дзнеладзе, Давид Эльдарович Фосфатная композиция и её применение
WO1998048987A1 (fr) * 1997-04-25 1998-11-05 Solutia Inc. Materiaux cellulosiques resistant au feu et traitement rendant ces materiaux resistants au lavage
EE00444U1 (et) 2004-03-17 2004-07-15 Nargo Holding OÜ Fosforiühend
EE00549U1 (et) 2005-02-01 2005-10-17 Nikolajev Gennadi Pinnakaitse-kattematerjal
ITMI20051019A1 (it) * 2005-05-31 2006-12-01 Isagro Spa Composizioni fungicide sinergiche
US8227365B2 (en) * 2005-06-08 2012-07-24 Ramachandran Nageswaran Biocidal ceramic compositions, methods and articles of manufacture

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2010020256A2 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011086526A1 (fr) 2010-01-15 2011-07-21 Uusen, Tarvi Composition de phosphate de fer et procédé pour la préparation et l'utilisation de celle-ci
US9586070B2 (en) 2013-01-22 2017-03-07 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in solid materials
US9878190B2 (en) 2013-01-22 2018-01-30 Miraculum, Inc. Flame retardant and fire extinguishing product for fires in solid materials

Also Published As

Publication number Publication date
PL2334596T3 (pl) 2012-11-30
DK2334596T3 (da) 2012-09-24
BRPI0917821A2 (pt) 2017-06-20
ES2391753T3 (es) 2012-11-29
BRPI0917821B1 (pt) 2020-01-07
GB201104566D0 (en) 2011-05-04
CA2724190A1 (fr) 2010-02-25
CN102046526B (zh) 2014-05-14
WO2010020256A3 (fr) 2010-07-15
EE05408B1 (et) 2011-04-15
CA2724190C (fr) 2016-10-11
GB2475454A (en) 2011-05-18
EE200800055A (et) 2010-04-15
WO2010020256A2 (fr) 2010-02-25
EP2334596B1 (fr) 2012-07-04
CN102046526A (zh) 2011-05-04
US20110223258A1 (en) 2011-09-15

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